JP6407503B2 - Polishing composition - Google Patents
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- JP6407503B2 JP6407503B2 JP2011284285A JP2011284285A JP6407503B2 JP 6407503 B2 JP6407503 B2 JP 6407503B2 JP 2011284285 A JP2011284285 A JP 2011284285A JP 2011284285 A JP2011284285 A JP 2011284285A JP 6407503 B2 JP6407503 B2 JP 6407503B2
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- 238000005498 polishing Methods 0.000 title claims description 159
- 239000000203 mixture Substances 0.000 title claims description 104
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 72
- 229910052710 silicon Inorganic materials 0.000 claims description 72
- 239000010703 silicon Substances 0.000 claims description 72
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- 230000002209 hydrophobic effect Effects 0.000 claims description 45
- 239000006061 abrasive grain Substances 0.000 claims description 41
- 229920003169 water-soluble polymer Polymers 0.000 claims description 34
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 150000007524 organic acids Chemical class 0.000 claims description 19
- 229920005591 polysilicon Polymers 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 12
- -1 alcohol compound Chemical class 0.000 claims description 9
- 239000011164 primary particle Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011163 secondary particle Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims 1
- 239000008119 colloidal silica Substances 0.000 description 26
- 230000002378 acidificating effect Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 230000007423 decrease Effects 0.000 description 9
- 229910052581 Si3N4 Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
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- 239000006087 Silane Coupling Agent Substances 0.000 description 3
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- 150000001298 alcohols Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 230000003628 erosive effect Effects 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 150000004804 polysaccharides Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000001879 Curdlan Substances 0.000 description 1
- 229920002558 Curdlan Polymers 0.000 description 1
- 229920002230 Pectic acid Polymers 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 108010020346 Polyglutamic Acid Proteins 0.000 description 1
- 108010039918 Polylysine Proteins 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 150000004781 alginic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 235000019316 curdlan Nutrition 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- LCLHHZYHLXDRQG-ZNKJPWOQSA-N pectic acid Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)O[C@H](C(O)=O)[C@@H]1OC1[C@H](O)[C@@H](O)[C@@H](OC2[C@@H]([C@@H](O)[C@@H](O)[C@H](O2)C(O)=O)O)[C@@H](C(O)=O)O1 LCLHHZYHLXDRQG-ZNKJPWOQSA-N 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
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- 239000010318 polygalacturonic acid Substances 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
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- 239000011550 stock solution Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Description
本発明は、疎水性のケイ素含有部分と親水性のケイ素含有部分とを有する研磨対象物の研磨に適した研磨用組成物に関する。本発明はまた、その研磨用組成物を用いた研磨方法及び基板の製造方法に関する。 The present invention relates to a polishing composition suitable for polishing an object to be polished having a hydrophobic silicon-containing portion and a hydrophilic silicon-containing portion. The present invention also relates to a polishing method and a substrate manufacturing method using the polishing composition.
従来、半導体装置の銅等の金属配線を形成するための化学的機械的研磨において、ファング（あるいはシーム）と呼ばれる欠陥が研磨後に生じることが問題となっており、このような欠陥の発生を防ぐ目的で、特許文献１〜５に開示されているような研磨用組成物の開発が行われている。 Conventionally, in chemical mechanical polishing for forming a metal wiring such as copper of a semiconductor device, a defect called a fang (or seam) has occurred after polishing, and the occurrence of such a defect is prevented. For this purpose, polishing compositions as disclosed in Patent Documents 1 to 5 have been developed.
一方、半導体装置のプラグ（コンタクトプラグ）やパッド（コンタクトパッド）を、化学的機械的研磨を通じてポリシリコン（多結晶ケイ素）から形成することが行われている。このようなプラグやパッドの形成に際しては一般に、ポリシリコンからなる部分に加えて、その周辺に設けられている酸化シリコン又は窒化シリコンからなる部分も同時に研磨をすることが必要である。この場合、金属配線の形成時と同様のファングに加え、エッジオーバーエロージョン（以下、ＥＯＥという）と呼ばれる欠陥も研磨後に生じることがある。このファング及びＥＯＥの発生は、ポリシリコン部分が疎水性であるのに対して酸化シリコン部分又は窒化シリコン部分が親水性であることが原因と考えられる。なお、ここでいうファングとは、ポリシリコン部分と酸化シリコン部分又は窒化シリコン部分との境界で局所的なエロージョンが起こることをいい、特に比較的幅広のポリシリコン部分の両脇で見られるものである。一方、ＥＯＥとは、比較的幅狭のポリシリコン部分があまり間隔を空けずに並んだ領域の両脇で局所的なエロージョンが起こることをいう。また同時に、ファングやＥＯＥに加えて、ポリシリコン部分が必要以上に研磨除去されることによりポリシリコン部分の上面のレベルが低下して皿状の凹み、すなわちディッシングが生じるという問題もある。このようなポリシリコンからなるプラグやパッドの形成に際してのファングやＥＯＥ、ディッシングなどの欠陥の発生は、特許文献１〜５の研磨用組成物を使用しても防止することは難しい。 On the other hand, plugs (contact plugs) and pads (contact pads) of semiconductor devices are formed from polysilicon (polycrystalline silicon) through chemical mechanical polishing. In forming such plugs and pads, it is generally necessary to simultaneously polish a portion made of silicon oxide or silicon nitride provided in the periphery of the portion made of polysilicon. In this case, a defect called edge over erosion (hereinafter referred to as EOE) may occur after polishing in addition to the fang similar to that at the time of forming the metal wiring. The occurrence of the fang and EOE is considered to be caused by the fact that the polysilicon portion is hydrophobic while the silicon oxide portion or the silicon nitride portion is hydrophilic. Here, the fang means that local erosion occurs at the boundary between the polysilicon portion and the silicon oxide portion or the silicon nitride portion, and is particularly seen on both sides of the relatively wide polysilicon portion. is there. On the other hand, EOE means that local erosion occurs on both sides of a region where polysilicon portions having relatively narrow widths are lined up without much interval. At the same time, in addition to fang and EOE, there is also a problem that the level of the upper surface of the polysilicon portion is lowered due to unnecessary polishing and removal of the polysilicon portion, resulting in dish-shaped dents, that is, dishing. It is difficult to prevent the occurrence of defects such as fang, EOE, dishing and the like when forming plugs and pads made of polysilicon, even if the polishing compositions of Patent Documents 1 to 5 are used.
そこで本発明の目的は、疎水性のケイ素含有部分と親水性のケイ素含有部分とを有する研磨対象物を研磨する用途で好適に用いることができる研磨用組成物を提供すること、またその研磨用組成物を用いた研磨方法及び基板の製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a polishing composition that can be suitably used in applications for polishing a polishing object having a hydrophobic silicon-containing portion and a hydrophilic silicon-containing portion, and for polishing the same. An object of the present invention is to provide a polishing method and a substrate manufacturing method using the composition.
上記の目的を達成するために、本発明の第１の態様では、親水性基を有する水溶性重合体、砥粒として有機酸を固定化したシリカ、及び酸を含有し、ｐＨ６以下である研磨用組成物を提供する。研磨用組成物を用いて疎水性のケイ素含有部分と親水性のケイ素含有部分とを有する研磨対象物を研磨した後の疎水性のケイ素含有部分の水接触角は、この研磨用組成物から水溶性重合体を除いた組成を有する別の組成物を用いて同じ研磨対象物を研磨した後の疎水性のケイ素含有部分の水接触角と比較して小さく、好ましくは５７度以下である。また、砥粒の平均二次粒子径の値を平均一次粒子径の値で除することにより得られる砥粒の平均会合度は１．２以上且つ４以下である。 In order to achieve the above object, in the first aspect of the present invention, a water-soluble polymer having a hydrophilic group, silica having an organic acid immobilized as abrasive grains , and an acid, and polishing having a pH of 6 or less A composition is provided. The water contact angle of the hydrophobic silicon-containing portion after polishing a polishing object having a hydrophobic silicon-containing portion and a hydrophilic silicon-containing portion using the polishing composition is determined from the polishing composition. Is smaller than the water contact angle of the hydrophobic silicon-containing part after polishing the same object to be polished using another composition having a composition excluding the conductive polymer, preferably 57 degrees or less. Moreover, the average degree of association of the abrasive grains obtained by dividing the value of the average secondary particle diameter of the abrasive grains by the value of the average primary particle diameter is 1.2 or more and 4 or less.
水溶性重合体が有する親水性基の数は一分子当たり３個以上であることが好ましい。
水溶性重合体は、多糖類又はアルコール化合物であること、特にポリエーテルであることが好ましい。
The number of hydrophilic groups contained in the water-soluble polymer is preferably 3 or more per molecule.
The water-soluble polymer is preferably a polysaccharide or an alcohol compound, particularly preferably a polyether.
水溶性重合体の分子量は、１０００以上であることが好ましい。
研磨用組成物は、疎水性のケイ素含有部分と親水性のケイ素含有部分とを有する研磨対象物であって、前記疎水性のケイ素含有部分と親水性のケイ素含有部分を同時に研磨する用途で使用される。疎水性のケイ素含有部分は例えばポリシリコンからなる。
The molecular weight of the water-soluble polymer is preferably 1,000 or more.
The polishing composition is a polishing object having a hydrophobic silicon-containing portion and a hydrophilic silicon-containing portion, and is used for polishing the hydrophobic silicon-containing portion and the hydrophilic silicon-containing portion at the same time. Is done. The hydrophobic silicon-containing portion is made of, for example, polysilicon.
本発明の第２の態様では、上記第１の態様の研磨用組成物を用いて、疎水性のケイ素含有部分と親水性のケイ素含有部分とを有する研磨対象物であって、前記疎水性のケイ素含有部分と親水性のケイ素含有部分を同時に研磨する方法を提供する。
本発明の第３の態様では、上記第１の態様の研磨用組成物を用いて、疎水性のケイ素含有部分と親水性のケイ素含有部分とを有する研磨対象物であって、前記疎水性のケイ素含有部分と親水性のケイ素含有部分を同時に研磨することにより、基板を製造する方法を提供する。
In a second aspect of the present invention, a polishing object having a hydrophobic silicon-containing portion and a hydrophilic silicon-containing portion using the polishing composition of the first aspect , wherein the hydrophobic A method for simultaneously polishing a silicon-containing portion and a hydrophilic silicon-containing portion is provided.
In a third aspect of the present invention, a polishing object having a hydrophobic silicon-containing portion and a hydrophilic silicon-containing portion using the polishing composition of the first aspect , wherein the hydrophobic Provided is a method of manufacturing a substrate by simultaneously polishing a silicon-containing portion and a hydrophilic silicon-containing portion .
本発明によれば、疎水性のケイ素含有部分と親水性のケイ素含有部分とを有する研磨対象物を研磨する用途で好適に用いることができる研磨用組成物と、その研磨用組成物を用いた研磨方法及び基板の製造方法とが提供される。 According to the present invention, a polishing composition that can be suitably used for polishing an object to be polished having a hydrophobic silicon-containing portion and a hydrophilic silicon-containing portion, and the polishing composition are used. A polishing method and a substrate manufacturing method are provided.
以下、本発明の一実施形態を説明する。
本実施形態の研磨用組成物は、砥粒及び水溶性重合体を水に混合することにより調製される。従って、研磨用組成物は、砥粒及び水溶性重合体を含有する。
Hereinafter, an embodiment of the present invention will be described.
The polishing composition of this embodiment is prepared by mixing abrasive grains and a water-soluble polymer with water. Accordingly, the polishing composition contains abrasive grains and a water-soluble polymer.
この研磨用組成物は、疎水性のケイ素含有部分と親水性のケイ素含有部分とを有する研磨対象物を研磨する用途、さらに言えばその研磨対象物を研磨して基板を製造する用途で使用される。疎水性のケイ素含有部分は、例えばポリシリコンからなるものである。親水性のケイ素含有部分は、例えば酸化シリコン又は窒化シリコンからなるものである。本実施形態の研磨用組成物を用いてそのような研磨対象物を研磨した場合には、疎水性のケイ素含有部分の表面に研磨用組成物中の水溶性重合体が吸着することにより当該表面の濡れ性が向上する結果、ファング及びＥＯＥの発生を抑えることができ、場合によってはさらにディッシングの発生も抑えることができる。 This polishing composition is used for polishing a polishing object having a hydrophobic silicon-containing portion and a hydrophilic silicon-containing portion, and more specifically, used for polishing a polishing object to produce a substrate. The The hydrophobic silicon-containing portion is made of, for example, polysilicon. The hydrophilic silicon-containing portion is made of, for example, silicon oxide or silicon nitride. When such a polishing object is polished using the polishing composition of the present embodiment, the surface of the hydrophobic silicon-containing portion is adsorbed by the water-soluble polymer in the polishing composition. As a result of the improved wettability, the occurrence of fangs and EOE can be suppressed, and in some cases, the occurrence of dishing can be further suppressed.
本実施形態の研磨用組成物は、このように金属を研磨する用途での使用を意図していないため、金属研磨用の組成物に通常含まれている酸化剤や金属防食剤のような成分を含有してはいない。 Since the polishing composition of this embodiment is not intended for use in applications for polishing metals in this way, components such as oxidizing agents and metal anticorrosive agents that are usually contained in metal polishing compositions It does not contain.
研磨用組成物中に含まれる水溶性重合体は、ヒドロキシ基、カルボキシ基、アミノ基及びエーテル基等の親水性基を有するものである。具体的には例えば、多糖類、アルコール化合物、ポリエーテル、ポリカルボン酸及びその塩等が使用可能である。あるいは、ポリオキシアルキレン鎖を有するノニオン性化合物も使用が可能である。 The water-soluble polymer contained in the polishing composition has a hydrophilic group such as a hydroxy group, a carboxy group, an amino group, and an ether group. Specifically, for example, polysaccharides, alcohol compounds, polyethers, polycarboxylic acids and salts thereof can be used. Alternatively, a nonionic compound having a polyoxyalkylene chain can also be used.
水溶性重合体が有する親水性基の数は、一分子当たり３個以上であることが好ましく、より好ましくは５個以上、さらに好ましくは１０個以上である。水溶性重合体が有する親水性基の数が多いほど、研磨対象物、特に疎水性のケイ素含有部分に対する親水効果が高まり、その結果としてファング及びＥＯＥの発生、場合によってはさらにディッシングの発生をより抑えることができる。 The number of hydrophilic groups contained in the water-soluble polymer is preferably 3 or more per molecule, more preferably 5 or more, and still more preferably 10 or more. As the number of hydrophilic groups in the water-soluble polymer increases, the hydrophilic effect on the object to be polished, particularly the hydrophobic silicon-containing portion, increases, and as a result, generation of fangs and EOE, and in some cases, more dishing. Can be suppressed.
また、水溶性重合体は、研磨用組成物を用いて疎水性のケイ素含有部分と親水性のケイ素含有部分とを有する研磨対象物を研磨した後の疎水性のケイ素含有部分の水接触角が、この研磨用組成物から水溶性重合体を除いた組成を有する別の組成物を用いて同じ研磨対象物を研磨した後の疎水性のケイ素含有部分の水接触角と比較して小さくなるような種類の化合物、好ましくは５７度以下、より好ましくは５０度以下、さらに好ましくは４５度以下となるような種類の化合物の中から選択して使用される。研磨用組成物を用いて研磨後の疎水性のケイ素含有部分の水接触角が小さくなるほど、ファング及びＥＯＥの発生、場合によってはさらにディッシングの発生をより抑えることができる。 Further, the water-soluble polymer has a water contact angle of the hydrophobic silicon-containing portion after polishing a polishing object having a hydrophobic silicon-containing portion and a hydrophilic silicon-containing portion using the polishing composition. The water contact angle of the hydrophobic silicon-containing portion after polishing the same object to be polished using another composition having a composition excluding the water-soluble polymer from the polishing composition is reduced. It is selected from various types of compounds, preferably 57 degrees or less, more preferably 50 degrees or less, and even more preferably 45 degrees or less. The smaller the water contact angle of the hydrophobic silicon-containing part after polishing with the polishing composition, the more the generation of fangs and EOE, and in some cases, the occurrence of dishing can be further suppressed.
このような水溶性重合体の具体例としては、多糖類であるアルギン酸、ペクチン酸、カルボキシメチルセルロース、デンプン、寒天、カードラン及びプルラン、
アルコール化合物であるポリエチレングリコール、ポリグリセリン、ペンタノール、ポリプロピレングリコール及びポリビニルアルコール（このうちポリエチレングリコール、ポリグリセリン及びポリプロピレングリコールはアルコール化合物であってかつポリエーテルである）、
ポリオキシアルキレン鎖を有するノニオン性化合物であるポリオキシエチレン（以下、ＰＯＥという）アルキレンジグリセルエーテル、ＰＯＥアルキルエーテル及びモノオレイン酸ＰＯＥ（６）ソルビタン、
ポリカルボン酸又はその塩であるポリアスパラギン酸、ポリグルタミン酸、ポリリシン、ポリリンゴ酸、ポリメタクリル酸、ポリメタクリル酸アンモニウム塩、ポリメタクリル酸ナトリウム塩、ポリマレイン酸、ポリイタコン酸、ポリフマル酸、ポリ（ｐ−スチレンカルボン酸）、ポリアクリル酸、ポリアクリルアミド、アミノポリアクリルアミド、ポリアクリル酸メチル、ポリアクリル酸エチル、ポリアクリル酸アンモニウム塩、ポリアクリル酸ナトリウム塩、ポリアミド酸、ポリアミド酸アンモニウム塩、ポリアミド酸ナトリウム塩、ポリグリオキシル酸、ポリカルボン酸アミド、ポリカルボン酸エステル及びポリカルボン酸塩が挙げられる。
Specific examples of such water-soluble polymers include polysaccharides such as alginic acid, pectic acid, carboxymethylcellulose, starch, agar, curdlan and pullulan,
Polyethylene glycol, polyglycerin, pentanol, polypropylene glycol and polyvinyl alcohol which are alcohol compounds (of which polyethylene glycol, polyglycerin and polypropylene glycol are alcohol compounds and polyethers),
Polyoxyethylene (hereinafter referred to as POE) alkylene diglyceryl ether, POE alkyl ether and monooleic acid POE (6) sorbitan, which are nonionic compounds having a polyoxyalkylene chain,
Polycarboxylic acid or its salt, polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, polymethacrylic acid, polymethacrylic acid ammonium salt, polymethacrylic acid sodium salt, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrene) Carboxylic acid), polyacrylic acid, polyacrylamide, aminopolyacrylamide, polymethyl acrylate, polyethyl acrylate, polyacrylic acid ammonium salt, polyacrylic acid sodium salt, polyamic acid, polyamic acid ammonium salt, polyamic acid sodium salt, Examples include polyglyoxylic acid, polycarboxylic acid amide, polycarboxylic acid ester, and polycarboxylic acid salt.
研磨用組成物中の水溶性重合体の含有量は１０質量ｐｐｍ以上であることが好ましく、より好ましくは５０質量ｐｐｍ以上、さらに好ましくは１００質量ｐｐｍ以上である。水溶性重合体の含有量が多くなるにつれて、研磨用組成物を用いて研磨後の疎水性のケイ素含有部分の水接触角が小さくなり、その結果としてファング及びＥＯＥの発生、場合によってはさらにディッシングの発生をより抑えることができる。 The content of the water-soluble polymer in the polishing composition is preferably 10 ppm by mass or more, more preferably 50 ppm by mass or more, and still more preferably 100 ppm by mass or more. As the water-soluble polymer content increases, the water contact angle of the hydrophobic silicon-containing portion after polishing with the polishing composition decreases, resulting in the occurrence of fangs and EOE, and in some cases dishing further Can be further suppressed.
研磨用組成物中の水溶性重合体の含有量はまた、１０００００質量ｐｐｍ以下であることが好ましく、より好ましくは５００００質量ｐｐｍ以下、さらに好ましくは１００００質量ｐｐｍ以下である。水溶性重合体の含有量が少なくなるにつれて、研磨用組成物中の砥粒の凝集が起こりにくくなり、その結果として研磨用組成物の保存安定性が向上する有利がある。 The content of the water-soluble polymer in the polishing composition is also preferably 100000 ppm by mass or less, more preferably 50000 ppm by mass or less, and still more preferably 10,000 ppm by mass or less. As the content of the water-soluble polymer decreases, the aggregation of abrasive grains in the polishing composition is less likely to occur. As a result, there is an advantage that the storage stability of the polishing composition is improved.
水溶性重合体の分子量は１００以上であることが好ましく、より好ましくは３００以上である。水溶性重合体の分子量が大きくなるにつれて、疎水性のケイ素含有部分の表面に水溶性重合体が効果的に吸着することができ、その結果として研磨用組成物を用いて研磨後の疎水性のケイ素含有部分の水接触角がより小さくなる有利がある。 The molecular weight of the water-soluble polymer is preferably 100 or more, more preferably 300 or more. As the molecular weight of the water-soluble polymer increases, the water-soluble polymer can be effectively adsorbed on the surface of the hydrophobic silicon-containing portion, and as a result, the hydrophobic property after polishing using the polishing composition can be reduced. There is an advantage that the water contact angle of the silicon-containing part becomes smaller.
水溶性重合体の分子量は５０００００以下であることが好ましく、より好ましくは３０００００以下である。水溶性重合体の分子量が小さくなるにつれて、研磨用組成物中の砥粒の凝集が起こりにくくなり、その結果として研磨用組成物の保存安定性が向上する有利がある。 The molecular weight of the water-soluble polymer is preferably 500,000 or less, more preferably 300,000 or less. As the molecular weight of the water-soluble polymer decreases, the aggregation of abrasive grains in the polishing composition is less likely to occur, and as a result, the storage stability of the polishing composition is advantageously improved.
研磨用組成物中に含まれる砥粒は、無機粒子、有機粒子、及び有機無機複合粒子のいずれであってもよい。無機粒子の具体例としては、例えば、シリカ、アルミナ、セリア、チタニアなどの金属酸化物からなる粒子、並びに窒化ケイ素粒子、炭化ケイ素粒子及び窒化ホウ素粒子が挙げられる。有機粒子の具体例としては、例えばポリメタクリル酸メチル（ＰＭＭＡ）粒子が挙げられる。その中でもシリカ粒子が好ましく、特に好ましいのはコロイダルシリカである。 The abrasive grains contained in the polishing composition may be any of inorganic particles, organic particles, and organic-inorganic composite particles. Specific examples of the inorganic particles include particles made of metal oxides such as silica, alumina, ceria, titania, and silicon nitride particles, silicon carbide particles, and boron nitride particles. Specific examples of the organic particles include polymethyl methacrylate (PMMA) particles. Among these, silica particles are preferable, and colloidal silica is particularly preferable.
砥粒は表面修飾されていてもよい。通常のコロイダルシリカは、酸性条件下でゼータ電位の値がゼロに近いために、酸性条件下ではシリカ粒子同士が互いに電気的に反発せず凝集を起こしやすい。これに対し、酸性条件でもゼータ電位が比較的大きな負の値を有するように表面修飾された砥粒は、酸性条件下においても互いに強く反発して良好に分散する結果、研磨用組成物の保存安定性を向上させることになる。このような表面修飾砥粒は、例えば、アルミニウム、チタン又はジルコニウムなどの金属あるいはそれらの酸化物を砥粒と混合して砥粒の表面にドープさせることにより得ることができる。 The abrasive grains may be surface-modified. Since ordinary colloidal silica has a zeta potential value close to zero under acidic conditions, silica particles are not electrically repelled with each other under acidic conditions and are likely to agglomerate. On the other hand, abrasive grains whose surfaces are modified so that the zeta potential has a relatively large negative value even under acidic conditions are strongly repelled from each other and dispersed well even under acidic conditions, resulting in storage of the polishing composition. Stability will be improved. Such surface-modified abrasive grains can be obtained, for example, by mixing a metal such as aluminum, titanium or zirconium or an oxide thereof with the abrasive grains and doping the surface of the abrasive grains.
あるいは、研磨用組成物中の表面修飾砥粒は、有機酸を固定化したシリカであってもよい。中でも有機酸を固定化したコロイダルシリカを好ましく使用することができる。コロイダルシリカへの有機酸の固定化は、コロイダルシリカの表面に有機酸の官能基を化学的に結合させることにより行われる。コロイダルシリカと有機酸を単に共存させただけではコロイダルシリカへの有機酸の固定化は果たされない。有機酸の一種であるスルホン酸をコロイダルシリカに固定化するのであれば、例えば、“Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups”, Chem. Commun. 246-247 (2003)に記載の方法で行うことができる。具体的には、３−メルカプトプロピルトリメトキシシラン等のチオール基を有するシランカップリング剤をコロイダルシリカにカップリングさせた後に過酸化水素でチオール基を酸化することにより、スルホン酸が表面に固定化されたコロイダルシリカを得ることができる。あるいは、カルボン酸をコロイダルシリカに固定化するのであれば、例えば、“Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel”, Chemistry Letters, 3, 228-229 (2000)に記載の方法で行うことができる。具体的には、光反応性２−ニトロベンジルエステルを含むシランカップリング剤をコロイダルシリカにカップリングさせた後に光照射することにより、カルボン酸が表面に固定化されたコロイダルシリカを得ることができる。 Alternatively, the surface-modified abrasive grains in the polishing composition may be silica with an organic acid immobilized thereon. Of these, colloidal silica having an organic acid immobilized thereon can be preferably used. The organic acid is immobilized on the colloidal silica by chemically bonding a functional group of the organic acid to the surface of the colloidal silica. If the colloidal silica and the organic acid are simply allowed to coexist, the organic acid is not fixed to the colloidal silica. If sulfonic acid, which is a kind of organic acid, is immobilized on colloidal silica, for example, a method described in “Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups”, Chem. Commun. 246-247 (2003). It can be carried out. Specifically, a silane coupling agent having a thiol group such as 3-mercaptopropyltrimethoxysilane is coupled to colloidal silica, and then the sulfonic acid is immobilized on the surface by oxidizing the thiol group with hydrogen peroxide. The colloidal silica thus obtained can be obtained. Alternatively, if the carboxylic acid is immobilized on colloidal silica, for example, “Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel”, Chemistry Letters, 3, 228- 229 (2000). Specifically, colloidal silica having a carboxylic acid immobilized on the surface can be obtained by irradiating light after coupling a silane coupling agent containing a photoreactive 2-nitrobenzyl ester to colloidal silica. .
研磨用組成物中の砥粒の含有量は０．１質量％以上であることが好ましく、より好ましくは０．５質量％以上、さらに好ましくは１質量％以上である。砥粒の含有量が多くなるにつれて、研磨用組成物による疎水性のケイ素含有部分及び親水性のケイ素含有部分の除去速度が向上する有利がある。 The content of abrasive grains in the polishing composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. As the abrasive content increases, the removal rate of the hydrophobic silicon-containing portion and the hydrophilic silicon-containing portion by the polishing composition is advantageously improved.
研磨用組成物中の砥粒の含有量はまた、２０質量％以下であることが好ましく、より好ましくは１５質量％以下、さらに好ましくは１０質量％以下である。砥粒の含有量が少なくなるにつれて、研磨用組成物の材料コストを抑えることができるのに加え、砥粒の凝集が起こりにくい。また、研磨用組成物を用いて研磨対象物を研磨することによりスクラッチの少ない研磨面を得られやすい。 The content of abrasive grains in the polishing composition is also preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. As the content of the abrasive grains decreases, the material cost of the polishing composition can be reduced, and in addition, aggregation of the abrasive grains hardly occurs. Moreover, it is easy to obtain a polished surface with few scratches by polishing an object to be polished using the polishing composition.
砥粒の平均一次粒子径は５ｎｍ以上であることが好ましく、より好ましくは７ｎｍ以上、さらに好ましくは１０ｎｍ以上である。砥粒の平均一次粒子径が大きくなるにつれて、研磨用組成物による疎水性のケイ素含有部分及び親水性のケイ素含有部分の除去速度が向上する有利がある。なお、砥粒の平均一次粒子径の値は、例えば、ＢＥＴ法で測定される砥粒の比表面積に基づいて計算することができる。 The average primary particle diameter of the abrasive grains is preferably 5 nm or more, more preferably 7 nm or more, and further preferably 10 nm or more. As the average primary particle diameter of the abrasive grains increases, there is an advantage that the removal rate of the hydrophobic silicon-containing portion and the hydrophilic silicon-containing portion by the polishing composition is improved. In addition, the value of the average primary particle diameter of an abrasive grain can be calculated based on the specific surface area of the abrasive grain measured by BET method, for example.
砥粒の平均一次粒子径はまた、１００ｎｍ以下であることが好ましく、より好ましくは９０ｎｍ以下、さらに好ましくは８０ｎｍ以下である。砥粒の平均一次粒子径が小さくなるにつれて、研磨用組成物を用いて研磨対象物を研磨することによりスクラッチの少ない研磨面を得られやすい。 The average primary particle diameter of the abrasive grains is also preferably 100 nm or less, more preferably 90 nm or less, and still more preferably 80 nm or less. As the average primary particle diameter of the abrasive grains decreases, it is easy to obtain a polished surface with few scratches by polishing the object to be polished using the polishing composition.
砥粒の平均二次粒子径は１５０ｎｍ以下であることが好ましく、より好ましくは１２０ｎｍ以下、さらに好ましくは１００ｎｍ以下である。砥粒の平均二次粒子径の値は、例えば、レーザー光散乱法により測定することができる。 The average secondary particle diameter of the abrasive grains is preferably 150 nm or less, more preferably 120 nm or less, and still more preferably 100 nm or less. The value of the average secondary particle diameter of the abrasive grains can be measured by, for example, a laser light scattering method.
砥粒の平均二次粒子径の値を平均一次粒子径の値で除することにより得られる砥粒の平均会合度は１．２以上であることが好ましく、より好ましくは１．５以上である。砥粒の平均会合度が大きくなるにつれて、研磨用組成物による疎水性のケイ素含有部分及び親水性のケイ素含有部分の除去速度が向上する有利がある。 The average degree of association of the abrasive grains obtained by dividing the value of the average secondary particle diameter of the abrasive grains by the value of the average primary particle diameter is preferably 1.2 or more, more preferably 1.5 or more. . As the average degree of association of the abrasive grains increases, the removal rate of the hydrophobic silicon-containing part and the hydrophilic silicon-containing part by the polishing composition is advantageously improved.
砥粒の平均会合度はまた、４以下であることが好ましく、より好ましくは３以下、さらに好ましくは２以下である。砥粒の平均会合度が小さくなるにつれて、研磨用組成物を用いて研磨対象物を研磨することによりスクラッチの少ない研磨面を得られやすい。 The average degree of association of the abrasive grains is also preferably 4 or less, more preferably 3 or less, and still more preferably 2 or less. As the average degree of association of the abrasive grains decreases, it is easy to obtain a polished surface with few scratches by polishing the object to be polished using the polishing composition.
研磨用組成物のｐＨは１２以下であることが好ましく、より好ましくは１１以下、さらに好ましくは１０以下である。研磨用組成物のｐＨが小さくなるにつれて、研磨用組成物による疎水性のケイ素含有部分のエッチングが起こりにくくなり、その結果としてディッシングの発生をより抑えることができる。 It is preferable that pH of polishing composition is 12 or less, More preferably, it is 11 or less, More preferably, it is 10 or less. As the pH of the polishing composition decreases, etching of the hydrophobic silicon-containing portion by the polishing composition is less likely to occur, and as a result, the occurrence of dishing can be further suppressed.
研磨用組成物のｐＨを所望の値に調整するために必要に応じて使用されるｐＨ調整剤は酸及びアルカリのいずれであってもよく、また無機及び有機の化合物のいずれであってもよい。 The pH adjuster used as necessary to adjust the pH of the polishing composition to a desired value may be either acid or alkali, and may be any of inorganic and organic compounds. .
本実施形態によれば以下の作用及び効果が得られる。
・ 本実施形態の研磨用組成物に含まれている水溶性重合体は親水性基を有しているため、疎水性のケイ素含有部分の表面にこの水溶性重合体が吸着することにより当該表面の濡れ性を向上することができる。このことが、本実施形態の研磨用組成物を用いて疎水性のケイ素含有部分と親水性のケイ素含有部分とを有する研磨対象物を研磨した場合にファング及びＥＯＥの発生を抑えることができ、場合によってはさらにディッシングの発生も抑えることができる理由と考えられる。そのため、本実施形態の研磨用組成物は、そのような研磨対象物を研磨する用途で好適に使用することができる。
According to this embodiment, the following operations and effects can be obtained.
-Since the water-soluble polymer contained in the polishing composition of the present embodiment has a hydrophilic group, the water-soluble polymer adsorbs on the surface of the hydrophobic silicon-containing portion, so that the surface The wettability can be improved. This can suppress the occurrence of fang and EOE when a polishing object having a hydrophobic silicon-containing portion and a hydrophilic silicon-containing portion is polished using the polishing composition of the present embodiment. In some cases, it can be considered that the occurrence of dishing can be further suppressed. Therefore, the polishing composition of the present embodiment can be suitably used in applications for polishing such a polishing object.
・ 研磨用組成物のｐＨが酸性（例えばｐＨ６以下）であってかつ研磨用組成物中に含まれる砥粒として有機酸を固定化したコロイダルシリカを使用した場合には、ファング、ＥＯＥ及びディッシングの発生をさらに抑えることができる。その理由は、有機酸を固定化したコロイダルシリカのゼータ電位が酸性のｐＨ領域で負の値を示すのに対し、研磨対象物のポリシリコンなどの疎水性のケイ素含有部分のゼータ電位もまた酸性のｐＨ領域で負の値を示すためである。つまり、酸性のｐＨ領域では研磨用組成物中の砥粒が研磨対象物の疎水性のケイ素含有部分に対して電気的に反発し、その結果、砥粒による疎水性のケイ素含有部分の過剰研磨が原因のファング、ＥＯＥ及びディッシングは生じにくい。 When the polishing composition has an acidic pH (for example, pH 6 or less) and colloidal silica to which an organic acid is immobilized is used as abrasive grains contained in the polishing composition, the fang, EOE and dishing Occurrence can be further suppressed. The reason is that the zeta potential of colloidal silica immobilized with an organic acid shows a negative value in the acidic pH region, whereas the zeta potential of hydrophobic silicon-containing parts such as polysilicon of the object to be polished is also acidic. This is because a negative value is exhibited in the pH region. That is, in the acidic pH region, the abrasive grains in the polishing composition are electrically repelled with respect to the hydrophobic silicon-containing portion of the object to be polished, and as a result, excessive polishing of the hydrophobic silicon-containing portion by the abrasive grains is performed. Fang, EOE and dishing due to
・ 研磨用組成物のｐＨが酸性（例えばｐＨ６以下）であってかつ研磨用組成物中に含まれる砥粒として有機酸を固定化したコロイダルシリカを使用した場合には、研磨用組成物による研磨対象物の親水性のケイ素含有部分の研磨速度が向上する。その理由は、有機酸を固定化したコロイダルシリカのゼータ電位が酸性のｐＨ領域で負の値を示すのに対し、研磨対象物の酸化シリコンや窒化シリコンなどの親水性のケイ素含有部分のゼータ電位が酸性のｐＨ領域で正の値を示すためである。つまり、酸性のｐＨ領域では研磨用組成物中の砥粒が研磨対象物の親水性のケイ素含有部分に対して電気的に反発せず、その結果、砥粒による親水性のケイ素含有部分の機械的研磨が促進される。 When the polishing composition has an acidic pH (for example, pH 6 or lower) and colloidal silica having an organic acid immobilized thereon is used as abrasive grains contained in the polishing composition, polishing with the polishing composition The polishing rate of the hydrophilic silicon-containing part of the object is improved. The reason is that the zeta potential of colloidal silica immobilized with organic acid shows a negative value in the acidic pH region, whereas the zeta potential of hydrophilic silicon-containing parts such as silicon oxide and silicon nitride of the object to be polished. This is because it shows a positive value in an acidic pH region. In other words, in the acidic pH region, the abrasive grains in the polishing composition do not electrically repel the hydrophilic silicon-containing portion of the object to be polished, and as a result, the hydrophilic silicon-containing portion machined by the abrasive grains. Polishing is promoted.
・ 研磨用組成物中に含まれる砥粒として有機酸を固定化したコロイダルシリカを使用した場合には、長期にわたり優れた分散安定性を有する研磨用組成物が得られる。その理由は、有機酸を固定化したコロイダルシリカは、有機酸が固定化されていない通常のコロイダルシリカに比べて、研磨用組成物中でのゼータ電位の絶対値が大きい傾向があるためである。研磨用組成物中でのゼータ電位の絶対値が大きくなるにつれて、シリカ粒子同士の間の静電的斥力が強まるために、ファンデルワールス力による引力が原因のコロイダルシリカの凝集は起こりにくくなる。例えば酸性のｐＨ領域において、有機酸を固定化したコロイダルシリカのゼータ電位は一般に−１５ｍＶ以下の負の値を示すのに対し、通常のコロイダルシリカのゼータ電位はゼロに近い値を示す。 -When the colloidal silica which fix | immobilized the organic acid is used as an abrasive grain contained in polishing composition, the polishing composition which has the dispersion stability excellent over the long term is obtained. The reason is that colloidal silica in which an organic acid is immobilized tends to have a larger absolute value of zeta potential in the polishing composition than ordinary colloidal silica in which no organic acid is immobilized. . As the absolute value of the zeta potential in the polishing composition increases, electrostatic repulsion between the silica particles increases, so that colloidal silica aggregation due to attractive force due to van der Waals force hardly occurs. For example, in an acidic pH range, the zeta potential of colloidal silica immobilized with an organic acid generally shows a negative value of −15 mV or less, whereas the zeta potential of ordinary colloidal silica shows a value close to zero.
前記実施形態は次のように変更されてもよい。
・ 前記実施形態の研磨用組成物は、水溶性重合体を二種類以上含有してもよい。この場合、一部の水溶性重合体については必ずしも親水性基を有している必要はなく、また疎水性のケイ素含有部分の水接触角を小さくする作用を必ずしも有している必要もない。
The embodiment may be modified as follows.
-The polishing composition of the said embodiment may contain 2 or more types of water-soluble polymers. In this case, some water-soluble polymers do not necessarily have a hydrophilic group, and do not necessarily have an action of reducing the water contact angle of the hydrophobic silicon-containing portion.
・ 前記実施形態の研磨用組成物は、防腐剤のような公知の添加剤を必要に応じてさらに含有してもよい。
・ 前記実施形態の研磨用組成物は一液型であってもよいし、二液型を始めとする多液型であってもよい。
-Polishing composition of the said embodiment may further contain well-known additives like a preservative as needed.
The polishing composition of the above embodiment may be a one-component type or a multi-component type including a two-component type.
・ 前記実施形態の研磨用組成物は、研磨用組成物の原液を水で希釈することにより調製されてもよい。
次に、本発明の実施例及び比較例を説明する。
-The polishing composition of the said embodiment may be prepared by diluting the undiluted | stock solution of polishing composition with water.
Next, examples and comparative examples of the present invention will be described.
コロイダルシリカゾルを水で希釈し、ｐＨ調整剤として有機酸を添加してｐＨの値を３に調整することにより比較例１の研磨用組成物を調製した。コロイダルシリカゾルを水で希釈し、そこに水溶性重合体を加えた後、有機酸を添加してｐＨの値を３に調整することにより実施例１〜１２及び比較例２，３の研磨用組成物を調製した。各研磨用組成物中の水溶性重合体の詳細は表１に示すとおりである。 The polishing composition of Comparative Example 1 was prepared by diluting colloidal silica sol with water and adding an organic acid as a pH adjuster to adjust the pH value to 3. The colloidal silica sol was diluted with water, a water-soluble polymer was added thereto, an organic acid was added, and the pH value was adjusted to 3, whereby the polishing compositions of Examples 1 to 12 and Comparative Examples 2 and 3 were used. A product was prepared. Details of the water-soluble polymer in each polishing composition are as shown in Table 1.
なお、表１中には示していないが、実施例１〜１２及び比較例１〜３の研磨用組成物はいずれも、スルホン酸を固定化したコロイダルシリカ（平均一次粒子径３５ｎｍ、平均二次粒子径７０ｎｍ、平均会合度２）を５質量％含有している。 Although not shown in Table 1, the polishing compositions of Examples 1 to 12 and Comparative Examples 1 to 3 were all colloidal silica (average primary particle size 35 nm, average secondary) with sulfonic acid immobilized thereon. The particle size is 70 nm and the average degree of association 2) is 5% by mass.
実施例１〜１２及び比較例１〜３の各研磨用組成物を用いて、ポリシリコンからなる部分と高密度プラズマＣＶＤ酸化シリコンからなる部分とを有する直径２００ｍｍのpoly-Si/HDPパターンウェーハを、表３に示す条件で研磨した。このパターンウェーハの研磨は、ポリシリコン部分の上面が露出した後、１５秒だけさらに継続の後に終了させた。 Using the polishing compositions of Examples 1 to 12 and Comparative Examples 1 to 3, a poly-Si / HDP pattern wafer having a diameter of 200 mm having a portion made of polysilicon and a portion made of high-density plasma CVD silicon oxide Polishing was performed under the conditions shown in Table 3. The polishing of the patterned wafer was finished after further continuing for 15 seconds after the upper surface of the polysilicon portion was exposed.
研磨後の各パターンウェーハを純水でリンスし、乾燥空気を吹き付けて乾燥した後、市販の接触角評価装置を用いてθ／２法で、ポリシリコン部分の水接触角を測定した。その結果を表２の“水接触角”欄に示す。 Each pattern wafer after polishing was rinsed with pure water, dried by blowing dry air, and then the water contact angle of the polysilicon portion was measured by a θ / 2 method using a commercially available contact angle evaluation device. The results are shown in the “Water contact angle” column of Table 2.
研磨後の各パターンウェーハについて、１００μｍ幅のポリシリコン部分が１００μｍ間隔で形成されている領域で、原子間力顕微鏡を用いて、ファングの進行量及びディッシングの進行量を測定した。その結果を表２の“１００μｍ／１００μｍ領域”欄の“ファング進行量”欄及び“ディッシング進行量”欄に示す。 About each pattern wafer after grinding | polishing, the progress amount of the fang and the progress amount of dishing were measured using the atomic force microscope in the area | region in which the polysilicon part of a 100 micrometer width is formed at 100 micrometer space | interval. The results are shown in the “Fang progress” column and the “Dishing progress” column in the “100 μm / 100 μm region” column of Table 2.
同じく研磨後の各パターンウェーハについて、０．２５μｍ幅のポリシリコン部分が０．２５μｍ間隔で形成されている領域で、原子間力顕微鏡を用いて、ＥＯＥの進行量及びディッシングの進行量を測定した。その結果を表２の“０．２５μｍ／０．２５μｍ領域”欄の“ＥＯＥ進行量”欄及び“ディッシング進行量”欄に示す。 Similarly, for each patterned wafer after polishing, the amount of progress of EOE and the amount of dishing were measured using an atomic force microscope in a region where 0.25 μm wide polysilicon portions were formed at intervals of 0.25 μm. . The results are shown in the “EOE progress amount” column and the “Dishing progress amount” column in the “0.25 μm / 0.25 μm region” column of Table 2.
Claims (9)
親水性基を有する水溶性重合体、砥粒として有機酸を固定化したシリカ、及び酸を含有し、ｐＨ６以下であり、
前記研磨用組成物を用いて前記研磨対象物を研磨した後の疎水性のケイ素含有部分の水接触角が、前記研磨用組成物から水溶性重合体を除いた組成を有する別の組成物を用いて前記研磨対象物を研磨した後の疎水性のケイ素含有部分の水接触角と比較して小さく、
前記砥粒の平均二次粒子径の値を平均一次粒子径の値で除することにより得られる砥粒の平均会合度は１．２以上且つ４以下であることを特徴とする研磨用組成物。 A polishing composition having a hydrophobic silicon-containing portion and a hydrophilic silicon-containing portion, the polishing composition used for polishing the hydrophobic silicon-containing portion and the hydrophilic silicon-containing portion at the same time Because
A water-soluble polymer having a hydrophilic group, silica having an organic acid immobilized as abrasive grains , and an acid, and having a pH of 6 or less,
Another composition having a composition in which the water contact angle of the hydrophobic silicon-containing portion after polishing the polishing object using the polishing composition is obtained by removing the water-soluble polymer from the polishing composition. Compared to the water contact angle of the hydrophobic silicon-containing part after polishing the polishing object using,
A polishing composition, wherein the average degree of association of the abrasive grains obtained by dividing the average secondary particle diameter value of the abrasive grains by the average primary particle diameter value is 1.2 or more and 4 or less .
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| EP12800395.1A EP2722872A4 (en) | 2011-06-14 | 2012-05-31 | Polishing composition |
| SG10201604609WA SG10201604609WA (en) | 2011-06-14 | 2012-05-31 | Polishing Composition |
| CN201280029023.4A CN103620747B (en) | 2011-06-14 | 2012-05-31 | Composition for polishing |
| US14/123,889 US9640407B2 (en) | 2011-06-14 | 2012-05-31 | Polishing composition |
| PCT/JP2012/064046 WO2012172983A1 (en) | 2011-06-14 | 2012-05-31 | Polishing composition |
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